KR20100053679A - Microreactor and liquid phase chemical reaction method using the microreactor - Google Patents

Abstract

This invention provides a microreactor comprising a microchamber including a raw material introduction port and a product discharge port, and a liquid phase chemical reaction method using the microreactor. The microreactor is characterized in that solid catalysts are packed, in the microchamber, so as to align in a line in the longitudinal direction of the microchamber.

Description

Micro Reactor, and Liquid Chemical Reaction Method Using Micro Reactor {MICROREACTOR AND LIQUID PHASE CHEMICAL REACTION METHOD USING THE MICROREACTOR}

The present invention relates to a microreactor and a liquid phase chemical reaction method using the microreactor. More specifically, the present invention relates to a microreactor capable of chemically reacting at a high rate, and a high yield liquid phase chemical reaction method using the microreactor.

This application claims priority based on Japanese Patent Application No. 2007-267148 for which it applied to Japan on October 12, 2007, and uses the content here.

A micro reactor is a flow type reaction apparatus which performs chemical reaction in the space (micro channel) of the size of 1 mm or less per side. Since the microreactor has a high heat exchange efficiency compared with the conventional large scale reaction apparatus, heat removal in exothermic reaction is quick and the deflection of temperature distribution does not produce easily. In addition, when scale-up in an industrial process, it responds by increasing the number of microchannels, and it is easy to expand to industrial production.

A microreactor is manufactured by forming the groove | channel which becomes a flow path in a flat board | substrate by the photolithographic method etc., for example, and covering the lid | cover with the flat plate which has a raw material introduction port and a product discharge port on the board | substrate with which the groove was formed (patent document 1). Etc). The flow paths are classified into T-shape, J-shape, Y-shape, cyclone, filler and the like according to their shape. And a micro reactor is provided so that the flow path may be horizontal and chemically reacts in the horizontal flow path (micro chamber).

On the other hand, the use of microreactors in gas phase chemical reactions has a long history and many studies have been conducted. However, the use of microreactors for liquid phase chemical reactions has a long history and many challenges. For example, in the liquid phase chemical reaction by a microreactor, pressure loss is large and clogging may occur. In addition, in a reaction system in which gas is generated by the reaction, an assumed reaction time cannot be secured because the gas pushes out the contents, or a gas adheres to the surface of the catalyst to inhibit contact between the liquid raw material and the catalyst, thereby reducing the reaction rate. There was a case where it could not be increased.

In order to increase the contact area of the catalyst and the reaction raw material in the chemical reactor, a catalyst having a large specific surface area is generally used. For example, what supported the metal catalyst on the particulate-form carrier of the size smaller than the inner diameter of a chemical reactor is mentioned. However, when a solid catalyst having a particulate form is charged into a microchamber and subjected to liquid phase reaction, channeling (a thick flow path unexpectedly occurs in the catalyst packed layer, the raw material liquid flows only in the flow path, and the raw material liquid does not flow outside the flow path. ), The contact area between the reaction raw material and the catalyst was smaller than the design value, and the reaction rate was sometimes lowered.

Japanese Unexamined Patent Publication No. 2007-136345

An object of the present invention is to provide a microreactor capable of chemically reacting at a high rate, and a high yield liquid phase chemical reaction method using the microreactor.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, when the chemical reaction was performed using the micro reactor which makes the micro chamber arrange | position and fill a solid catalyst in a line in the chamber longitudinal direction, it discovered that the reaction rate becomes high. The present invention has been completed based on further findings.

That is, this invention includes the following aspects.

(1) A microreactor comprising a microchamber including a raw material inlet and a product outlet, wherein the microchamber is filled with a solid catalyst in a line in the longitudinal direction of the microchamber.

(2) The microreactor according to (1), wherein the solid catalyst is pellet-shaped, tablet-shaped, or disk-shaped.

(3) The solid catalyst is formed by supporting a catalyst containing a transition metal element and / or an acid or a transition metal element and / or a base on a pellet, tablet or disc-shaped carrier. (1) Micro reactor.

(4) A liquid phase chemical reaction method using the microreactor according to any one of (1) to (3), wherein a liquid phase raw material is introduced into a microchamber from a raw material inlet, and chemically reacted in a microchamber to obtain a product. A liquid chemical reaction method for discharging the product from the product outlet of the microreactor.

(5) The liquid phase chemical reaction method of (4), wherein the product contains a gaseous product.

When the microreactor of the present invention is used, chemical reaction can be performed at a high rate. When the liquid phase chemical reaction is carried out using the microreactor of the present invention, the product can be obtained in high yield. In the microreactor of the present invention, unexpected channeling is less likely to occur, and the contact area between the raw material and the solid catalyst is in accordance with the design value, thereby facilitating the design of the microreactor.

1 is a conceptual diagram illustrating an example of the microreactor of the present invention.
2 is a conceptual diagram showing another example of the microreactor of the present invention.
3 is a conceptual diagram illustrating a micro reactor when a solid catalyst is randomly charged.
4 is a conceptual diagram illustrating an example of a microreactor provided with a raw material supply device.

In this embodiment, a glass straight tube is used as the microchamber, and the solid catalyst (C1 or C2) is filled in a straight line as shown in FIG. 1 or 2 in the glass straight tube, and a microchannel is formed between the glass tube and the solid catalyst. The raw material compound was supplied from one end of the glass straight tube to react, and the desired product was extracted from the other end of the glass straight tube. The product obtained by the microreactor of the present invention may contain a gaseous by-product.

Although the reaction temperature suitable for the microreactor of this invention is not specifically limited, Although it can select suitably according to the chemical reaction performed, Specifically, the range of 25-250 degreeC can be illustrated, Preferably it is the range of 100-200 degreeC Can be illustrated. By setting it as this temperature range, control of reaction rate becomes easy.

The microreactor of the present invention comprises a microchamber including a raw material inlet and a product outlet, and is filled with a solid catalyst arranged in a line in the longitudinal direction of the microchamber.

In the present invention, the same one as the microchamber of the conventional microreactor is used as the microchamber. For example, glass tubes; Covering a lid with a flat plate on the board | substrate which formed the groove used as a flow path; Etc. can be mentioned. A raw material inlet is formed at at least one end of the microchamber, and a product outlet is formed at the other end, the raw material is supplied from the raw material inlet, and the product is taken out from the product outlet.

The microchamber can be made into an appropriate flow path layout depending on the number and type of raw materials provided to the chemical reaction. For example, a microchamber having a Y-shaped or T-shaped flow path may be prepared, two kinds of raw materials may be introduced from two inlets, and the two kinds of raw materials may be mixed and reacted at the flow path confluence unit. have. Moreover, a raw material can be introduced from one inlet, a homogeneous catalyst can be introduced from the other inlet, and the said raw material and a catalyst can be mixed and reacted in a flow path confluence part. The raw material to be introduced may be either a liquid phase or a gaseous phase, but it is preferable to use a liquid phase as a raw material in order to draw out the features of the microreactor of the present invention.

The volume of the microchamber is not particularly limited, and one side is preferably about 10 µm to about 5000 µm. Moreover, it is preferable that one side of the microchannel formed after filling a solid catalyst will be about 1 micrometer-about 1000 micrometers. If one side of the microchannel is too small, the pressure loss becomes high and it becomes difficult to supply the raw material. On the contrary, when too big | large, heat exchange efficiency will fall, temperature distribution etc. will generate | occur | produce, and the micro reactor will reduce the special feature. Although the flow path length of a microchamber is not specifically limited, It is preferable that it is 10-300 cm.

In the microreactor of the present invention, a solid catalyst is filled in the microchamber.

The solid catalyst may be a solidified powder of the catalyst or a supported catalyst formed by supporting the catalyst on a carrier.

The catalyst can be appropriately selected depending on the type of chemical reaction. Typical examples include catalysts containing transition metal elements and / or acids, or transition metal elements and / or bases.

Examples of the transition metal elements include tantalum, molybdenum, tungsten, ruthenium, osmium, palladium, nickel, iron, cobalt, chromium, rhodium, iridium, platinum, gold, silver, copper, titanium, niobium, and the like.

Examples of the catalyst containing an acid or a base include silica-alumina complex oxides, zeolites, Nb ₂ O ₅ —MoO ₃ complex oxides, Nb ₂ O ₅ nH ₂ O, proton-type strong acid bead-like fluorine-containing resins, Acid catalysts such as titania-silica composite oxides; And base catalysts such as magnesium dialkoxide, magnesium oxide, calcium oxide and sodium alkoxide.

Examples of the carrier include carbon, silica, silica-alumina, alumina, diatomaceous earth, calcium carbonate, zinc carbonate, barium carbonate, barium sulfate, strontium carbonate and the like. Moreover, the shape of a support | carrier is not limited, For example, a pellet shape, a tablet shape, disk shape, spherical shape, ring shape, mesh shape, honeycomb shape, indefinite shape, etc. are mentioned. It is preferable to form a pellet shape, a tablet shape, or disk shape among these. The size of the solid catalyst can be appropriately selected according to the inner diameter of the microchamber so that the solid catalysts are arranged in a line in the longitudinal direction of the microchamber. If the size of the solid catalyst becomes too small with respect to the inner diameter of the microchamber, the solid catalyst is arranged in two or more rows, so the size of the solid catalyst is preferably at least 70% of the inner diameter of the microchamber. In addition, "arranged in a line" is not limited to being arranged in a straight line, and may be arranged in a line by bending like a zigzag.

The solid catalysts are arranged in a line in the longitudinal direction of the microchamber and filled in the microchamber. For example, as shown in FIG. 1, the pellet-shaped (cylindrical) solid catalyst C1 was aligned and filled in line with the height direction of the cylinder in the longitudinal direction of the microchamber R1; As shown in FIG. 2, the spherical solid catalyst C2 is aligned in the longitudinal direction of the microchamber R2, and is arranged in a line and filled. By arranging in this manner, the raw materials mainly pass through the gap space (micro channel) between the solid catalyst and the inner wall of the microchamber. As a result, unexpected channeling is less likely to occur, and the contact area between the raw material and the solid catalyst is as designed, so that the design of the microreactor becomes easy. When the microchannel is straight along the glass tube, the product gas is likely to be pushed out to the product outlet even when gas is generated by the liquid phase chemical reaction. Moreover, by carrying and fixing the catalyst on the inner wall of the microchamber, the catalyst contacted by the raw material can be made both of the solid catalyst arranged in a line and the catalyst supported on the inner wall, so that the reaction efficiency can be further increased.

Although the usage-amount of a catalyst is not specifically limited, Although it can select suitably according to the supply amount of a raw material (reaction substrate), it is normally the range of 0.01-100 mol% with respect to a reaction substrate, Preferably it is the range of 0.1-50 mol%, More preferably, it is 0.1-10 mol% of range.

Moreover, it is preferable that the microreactor is equipped with the apparatus for supplying a raw material to a microchamber, for example, a pump. It is preferable that a raw material supply apparatus does not become a movement (pulse). Electro Osmotic Flow can also be used for normal delivery.

In this invention, a raw material may be supplied as it is to a micro reactor, may be dissolved in solvents, such as water, methanol, isopropyl ether, benzene, and hexane, and may be supplied to a micro reactor.

The feed amount (flow rate) per hour of the raw material can be appropriately selected depending on the amount of the catalyst, and can be usually selected in the range of 0.1 to 500 ml / h, preferably in the range of 0.5 to 50 ml / h, more preferably. Preferably it is the range of 1.0-5 ml / h.

Moreover, it is preferable to set it as 1-1000 mmol / h as a contact amount per 1 mol of catalysts, and, as for 1 hour of supply of a raw material, it is more preferable to set it as 10-160 mmol / h.

Example

Next, an Example is shown and this invention is demonstrated in detail. In addition, this invention is not limited to these Examples.

Reaction was performed using the apparatus shown in FIG. The microreactor (it described as MICROREACTOR in FIG. 4) used what packed the pellet which carried the catalyst of diameter 3mm and the length 3.5mm in the stainless steel tube of internal diameter 4mm in a line in the longitudinal direction. The pellet used what carried 0.5 weight% palladium on the surface of an alumina (made by NE Chemicat Co., Ltd.).

Example 1

As the microreactor, a tube having a total length of 150 mm filled with 2150 mg of pellets (43 pellets of 50 mg pellets and 0.85 mol% of supported palladium relative to the reaction substrate) was used. A solution obtained by dissolving 4.1 g (20 mmol) of iodine benzene and 2.0 g (20 mmol) of phenylacetylene in 3 mL of N, N-dimethylacetamide was charged into a gastite syringe, and the solution was charged at 1.0 mL / h at a temperature of 100 ° C. The reaction was carried out at a flow rate of 30 minutes. As a result of analyzing the obtained reaction liquid by high performance liquid chromatography, it was confirmed that the product was obtained quantitatively.

Example 2

As the microreactor, a tube having a total length of 150 mm filled with 2150 mg of pellets (43 pellets of 50 mg pellets and 0.85 mol% of supported palladium relative to the reaction substrate) was used. A gastight syringe was charged with a solution of 4.1 g (20 mmol) of iodine benzene, 2.1 g (24 mmol) of methyl acrylate, and 3.4 g (34 mmol) of triethylamine in 3 ml of N-methylpyrrolidone. The reaction was carried out at a temperature of 120 ° C., set at each flow rate and residence time shown in Table 1. Table 1 shows the results of analyzing the obtained reaction solution by high performance liquid chromatography.

Example 3

As the micro reactor, a tube having a total length of 250 mm filled with 3600 mg of pellets (72 pellets of 50 mg of one pellet and 0.85 mol% of supported palladium relative to the reaction substrate) was used. A mixture of benzaldehyde 2.1 g (20 mmol) and nitromethane 1.2 g (20 mmol) was charged in a gastite syringe, and the reaction was carried out at a temperature of 60 ° C at a flow rate of 2.2 ml / h for 1 hour. . The obtained reaction liquid was concentrated under reduced pressure, and the product was confirmed by ¹ H-NMR to give 2-nitro-1-phenyl-ethanol which was the target product almost quantitatively at a conversion rate of 18%.

Example 4

As the microreactor, a tube having a total length of 250 mm filled with 3600 mg of pellets (72 pellets of one 50 mg and 3.38 mol% of supported palladium relative to the reaction substrate) was used. A mixture of 528 mg (5 mmol) of phenylacetylene and 5 ml of allyl bromide (12 times mol equivalent to phenylacetylene) was charged into a gastite syringe, and the residence time was set at a flow rate of 1.1 ml / h at room temperature for 2 hours. The reaction was carried out. As a result of analyzing the obtained reaction liquid by gas chromatography, 1-bromo-1-phenyl-1,3-butadiene and 1-bromo-2-phenyl-1- which are target objects at a reaction conversion rate of 43% and a yield of about 90%. A mixture of butenes was obtained.

Comparative Example 1

As the micro reactor, a tube having a total length of 100 mm filled with alumina powder (supported Pd was 0.85 mol% equivalent to the reaction substrate) loaded with 0.5% by weight of palladium was used. In the same manner as in Example 1, a solution obtained by dissolving 4.1 g (20 mmol) of iodinebenzene and 2.0 g (20 mmol) of phenylacetylene in 3 ml of N, N-dimethylacetamide was charged into a gastite syringe, and the temperature was 100 ° C. The reaction was carried out at a flow rate of 0.1 mL / h at a residence time of 40 minutes. As a result of analyzing the obtained reaction liquid by high performance liquid chromatography, it was confirmed that the product was obtained quantitatively. However, as a result of setting the flow rate to 0.1 ml / h or more, the pressure loss increased, and the flow velocity could not be increased.

Compared to the microreactor (Comparative Example 1) in which the solid catalyst was randomly charged from the above Examples 1 to 4 and Comparative Example 1, the microreactor (Examples 1 to 4) formed by arranging and filling the solid catalysts in a row It can be seen that the pressure loss is small, so that the flow rate can be increased and the chemical reaction can be performed at high efficiency.

When the microreactor of the present invention is used, the pressure loss is small and the flow rate can be increased, so that the chemical reaction can be performed with high efficiency. In addition, when the liquid phase chemical reaction is carried out using the microreactor of the present invention, the product can be obtained in high yield. In addition, in the microreactor of the present invention, unexpected channeling is less likely to occur, and the contact area between the raw material and the solid catalyst is in accordance with the design value, which facilitates the design of the microreactor and is industrially useful.

R1, R2, R3: Micro Chamber
C1, C2: solid catalyst
In: Raw material introduction port
Out: Product outlet

Claims (5)

And a microchamber having a raw material inlet and a product outlet, wherein the microchamber is filled with the solid catalyst in a line in the longitudinal direction of the microchamber. The method of claim 1,
And the solid catalyst is pellet-shaped, tablet-shaped, or disk-shaped. The method of claim 1,
A microreactor, wherein the solid catalyst is formed by supporting a catalyst containing a transition metal element and / or an acid, or a transition metal element and / or a base on a pellet, tablet, or disc-shaped carrier. A liquid phase chemical reaction method using the microreactor according to any one of claims 1 to 3, wherein a liquid phase raw material is introduced into a microchamber from a raw material inlet, and chemically reacted in a microchamber to obtain a product. A liquid chemical reaction method for discharging the product from the product outlet of the reactor. The method of claim 4, wherein
Wherein said product comprises a gaseous product.

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